Aqueous organometallic chemistry: The mechanism of catalytic hydrogenations with chlorotris(1,3,5-triaza-7-phosphaadamantane) rhodium(I)

被引：67

作者：

Joo, F ^{[1
]}

Nadasdi, L ^{[1
]}

Benyei, AC ^{[1
]}

Darensbourg, DJ ^{[1
]}

机构：

[1] TEXAS A&M UNIV,DEPT CHEM,COLLEGE STN,TX 77843

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1996年 / 512卷 / 1-2期

基金：

匈牙利科学研究基金会; 美国国家科学基金会;

关键词：

rhodium; hydrogenation; phosphines;

D O I：

10.1016/0022-328X(95)05946-M

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The water-soluble phosphine complex of Rh(I), RhCl(PTA)(3) (1) was shown to be an active catalyst for the hydrogenation of various olefinic and oxo-acids, as well as of allyl alcohol and 4-sulfostyrene in aqueous solution under mild conditions. Detailed kinetic investigations were carried out with crotonic acid and allyl alcohol as substrates. The rate of hydrogenation of both compounds showed a sharp maximum as a function of pH at 4.7. Hydrogenation of itaconic, crotonic and alpha-acetamidocinnamic acid in D2O led to 45-100% deuteration of the products with 25-100% stereoselectivity towards the ct-carbon atom. These results, together with those of pH-static hydrogenation of complex 1, suggest that water strongly assists the dehydrochlorination of 1 to yield the catalytically active monohydrido species HRh(PTA)(3) (2). Nevertheless, depending on the substrate and the pH of the solution the dihydridic pathway may remain partially operative.

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页码：45 / 50

页数：6

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